CN106853296B - A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof - Google Patents
A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof Download PDFInfo
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- CN106853296B CN106853296B CN201611263274.5A CN201611263274A CN106853296B CN 106853296 B CN106853296 B CN 106853296B CN 201611263274 A CN201611263274 A CN 201611263274A CN 106853296 B CN106853296 B CN 106853296B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
Abstract
The present invention relates to a kind of oil water separation type sodium alginate/graphene oxide composite aerogels and preparation method thereof.A kind of preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel, including the preparation of sodium alginate/graphene oxide liquid mixture, the preparation of uncrosslinked sodium alginate/graphene oxide composite aerogel and the preparation of oil water separation type sodium alginate/graphene oxide composite aerogel.Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, with highly porous structure and perfect 3 D stereo network, separative efficiency is high, separation rate > 99.9%, and salt resistance ability is high, can be suitable for marine environment with high salt, also has good elasticity, higher mechanical strength and oil resistant pollution capacity, reusable 40 times or more and separative efficiency have good recycling ability almost without decline.
Description
Technical field
The present invention relates to a kind of oil water separation type composite aerogels and preparation method thereof, and in particular to a kind of oil water separation type
Sodium alginate/graphene oxide composite aerogel and preparation method thereof has salt tolerant, underwater superoleophobic and fuel sensitivity,
Belong to biomass-based functional material preparation technical field.
Background technique
In in the past few decades, Oil spills and chemical leakage accident take place frequently, and make to marine environment and the ecosystem
At significant damage.Thus, how to realize that oil-water efficiently separates the topic for having become global concern in marine environment.Oil-water
Separation belongs to the scope of field of interfaces, and it is to solve the problems, such as that this is effectively easy that developing, which has the functional material of superoleophobic characteristic,
Strategy.Up to now, the material with superoleophobic characteristic is all modified by fluorine containing silane reagent substantially in air, however,
The material of fluorine functional is easy to lose superoleophobic property in the seawater.The unique underwater superoleophobic characteristic of fish scale, is bionical structure
It builds underwater superoleophobic material such as hydrogel coating and inorganic metal oxide washcoat and opens new window.However, using this
The maximum challenge of material is that their environmental resistance ability is poor.It is impregnated by long-term seawater, they may be from substrate
It falls off or by dilatancy, it is caused to gradually lose superoleophobic property.In addition, there are step complexity, valence for current preparation method
The disadvantages of lattice are expensive, it is difficult to realize large-scale industrialization application.Therefore, it develops cheap, salt tolerance and can give birth on a large scale
The functional material of production realizes oil/water separation in marine environment, is very important.
Aeroge is a kind of solid material of high porosity, has lower density and three-dimensional net structure, is to prepare height
The good selection of flux, efficient Oil-water separation material.Sodium alginate is a kind of natural polysaccharide, it is present in the cell wall of brown alga,
It is made of beta-D-mannuronic acid and α-L- guluronic acid by β -1,4- glucosides key connection and by the segment of different proportion
Copolymer.Studies have shown that the aeroge prepared by this natural biologic material, has good salt tolerance and underwater superoleophobic property
Can, realizing marine environment Oil-water separation field with huge potentiality.However, want this material of large-scale application, still need to gram
Take two obstacles: 1) the lower problem of pure sodium alginate aeroge mechanical strength；2) it is related to complicated ion in preparation process
Crosslinking process does not utilize large-scale production.To improve aeroge mechanical strength, an effective method is exactly by Nano grade
Reinforcing filler is introduced into sodium alginate aeroge three-dimensional network.In aeroge preparation process, such as directly by divalent ion (such as calcium
Ion) it introduces sodium alginate soln and carries out ionomer, relatively it is also easy to produce anisotropic colloidal particle and sol solution heterogeneous.
Common practice is to introduce CaCO3- GDL(glucolactone) to reduce the rate of release of calcium ion.Although this mode can
To enable the sol solution generated more uniform, but practical operation is complex.
Summary of the invention
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of oil water separation type sodium alginate/oxidations
Graphene composite aerogel and preparation method thereof.The present invention is filled out graphene oxide enhancing based on sodium alginate aeroge
Material introduces inside sodium alginate aeroge three-dimensional network, by way of being simply freeze-dried and being combined with ionomer, structure
A kind of sodium alginate/graphene oxide composite aerogel is built, to realize the purpose of Oil-water separation, is used for marine environment or oil-containing
Oil-aqueous mixtures separation in waste water.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel of the invention, feature
It is that preparation step is as follows:
(1) sodium alginate/graphene oxide liquid mixture preparation:
A, prepare sodium alginate soln: sodium alginate be dissolved in deionized water, after 800 ~ 1200rpm magnetic agitation, 1 ~ 2h by
Mixing speed is gradually reduced to 500 rpm until it becomes clear solution, the sodium alginate that obtained concentration is 1wt% ~ 4wt% is molten
Liquid；
B, then 10 ~ 20min of graphene oxide suspension that ultrasonic treatment concentration is 0.5wt% ~ 3wt% is added to step
In sodium alginate soln obtained by rapid A, make graphene oxide and sodium alginate mass ratio 0.5:10 ~ 1:10,1200 ~ 2000rpm
Magnetic agitation is no less than 2h, obtains sodium alginate/graphene oxide dispersion；
(2) uncrosslinked sodium alginate/graphene oxide composite aerogel preparation: will be equipped with alginic acid obtained by step (1)
Sodium/graphene oxide dispersion vessel, are put into lyophilization system and are freeze-dried, and acquire uncrosslinked alginic acid
Sodium/graphene oxide composite aerogel.
(3) oil water separation type sodium alginate/graphene oxide composite aerogel preparation: will be uncrosslinked obtained by step (2)
Sodium alginate/graphene oxide composite aerogel be placed in concentration be 2wt% ~ 4wt% calcium chloride solution in, react 8 ~ 12h after,
Using the multiple repeated flushing aeroge of deionized water, secondary freeze drying is then carried out, obtains oil water separation type sodium alginate/oxygen
Graphite alkene composite aerogel.
The sodium alginate, as main body gel forming materials；Graphene oxide, as reinforcing filler；Calcium chloride solution,
In calcium ion play the role of cause crosslinking.
In the preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel of the present invention, each step is most
Good parameter is as follows:
Magnetic agitation optimum speed described in step (1) is 1000rpm, the best addition concentration of graphene oxide suspension
For 1 wt%, sodium alginate soln optium concentration is 2 wt%, and the graphene oxide and sodium alginate mass ratio are 1:10, institute
The sonication treatment time stated is 15min.
Step (2) vessel are culture dish, and freeze-drying temperature is -15 °C, and absolute pressure is 400 μ bar, and freezing is dry
The dry time is 48h.
Step (3) described calcium chloride solution, optium concentration are 4 wt%, and the time for immersing ionic calcium soln is 10h.
Oil water separation type sodium alginate/graphene oxide composite aerogel of the invention is as shown in Figure 1, its microscopic appearance knot
For structure as shown in Fig. 2, in Fig. 2, a is low range micro-structure diagram (× 50,500 μm), b be high magnification micro-structure diagram (× 1000,
10 μm)；Various oil products can be such as Fig. 3 institute in oil water separation type sodium alginate/graphene oxide composite aerogel wettability of the surface
Show.
Oil water separation type sodium alginate/graphene oxide composite aerogel performance test of the invention, the method is as follows:
(1) wettability is tested
Water and oil are commented using Drop Shape Analysis System by contact angle test in aeroge wettability of the surface energy
Estimate.
Air Zhong Shui and oil can be tested in aeroge wettability of the surface:
5 μ L water droplets and oil droplet (test oil are as follows: kerosene, pumping fluid, n-hexane, soybean oil and toluene) are taken to instill gas respectively
Gel surface is changed using the contact angle that Drop Shape Analysis System tracks water droplet and oil droplet, assesses its aerial wetting
Property.
Underwater oil can be tested in aeroge wettability of the surface:
Aeroge is immersed into simulated seawater, 17.2 g sea salt are dissolved in 500 mL deionized waters by the simulated seawater
In, with micro syringe by 5 μ L oil droplets (test oil are as follows: kerosene, pumping fluid, n-hexane, soybean oil and toluene) from aeroge
Bottom surface injection, by testing the underwater oil of size assessment of oil droplet contact angle in aeroge wettability of the surface.
(2) salt resistant character is tested
Aeroge is immersed into 30 days (being set as a cycle) in simulated seawater, every the primary underwater oil of test in 5 days in gas
The wettability of gel surface (taking kerosene is test oil), i.e., judge the anti-salt property of aeroge according to the variation of the contact angle of oil.
(3) oil-aqueous mixtures separative efficiency test
Firstly, aeroge surface is pre-wetted with water, then it is fixed between two vertical glass tubes and with folder
Sub-folder is lived, and connects liquid-collecting bottle below.Apparatus above is poured into configuration oil-aqueous mixtures (V:V=1:1), is imitated to the separation of oil water mixture
Rate is tested.Wherein, test oil product includes kerosene, pumping fluid, n-hexane, soybean oil, toluene and crude oil, and water is simulation sea
Water.Oil-aqueous mixtures separative efficiency then passes through the quality for calculating filtering front and back oil product, is determined by following formula:
η (%) = (m a/m b) × 100
Wherein,m bWithm aThe respectively quality of filtering front and back oil,ηFor oil-aqueous mixtures separative efficiency.
(4) reusing is tested
Oil-aqueous mixtures separation finishes, to oil water separation type sodium alginate/graphene oxide composite aerogel of the invention
It is repeatedly squeezed and is rubbed, and rinse aeroge oil droplet remained on surface with flowing water, it is mixed to continue on for oil-water next time
The separation process of object is closed, and separative efficiency is tested.
Advantages of the present invention and the utility model has the advantages that compared with prior art, the invention has the advantages that grease of the invention
Divergence type sodium alginate/graphene oxide composite aerogel has highly porous structure and perfect 3 D stereo network, table
Reveal excellent Oil-water separation efficiency.The aeroge also has good elasticity, higher mechanical strength and oil resistant pollution capacity,
Reusable 40 times or more and separative efficiency are almost without decline.
Advantages of the present invention is as follows:
(1) oil water separation type of the invention sodium alginate/graphene oxide composite aerogel has highly porous knot
Structure, this structure are conducive to the separation of oil-aqueous mixtures, separative efficiency > 99.9%, separative efficiency through entire three-dimensional network
It is high.
(2) oil water separation type of the invention sodium alginate/graphene oxide composite aerogel, salt tolerant energy with higher
Power has expanded aeroge in the scope of application in Oil-water separation field, can be suitable for marine environment with high salt.
(3) oil water separation type of the invention sodium alginate/graphene oxide composite aerogel has good elasticity and machine
Tool intensity is repeatedly rubbed, squeezes and can restore to the original state rapidly and structure is without damage, is conducive to the multiple circulation of aeroge
It recycles.
(4) oil water separation type of the invention sodium alginate/graphene oxide composite aerogel has underwater superoleophobic property
Can, oily contact angle is up to 166 °, is demonstrated by unique oil resistant pollution capacity.Oil-aqueous mixtures separation finishes, aeroge surface
Remaining oil droplet only needs clear water flushing that can continue to use, has good recycling ability without chemical reagent processing.
The present invention selects to be added into very good mechanical properties and the graphene oxide of significant flexibility as reinforcing filler
Sodium alginate soln prepares compound sodium alginate/graphene oxide composite aerogel, and the introducing of graphene oxide can be effective
Ground shifts the load that sodium alginate matrix is born, and can construct the more excellent three-dimensional network skeleton of mechanical performance.Meanwhile the present invention
It proposes a kind of simpler preparation process, i.e., sodium alginate/graphene oxide mixed solution is freeze-dried and is not handed over first
Then the composite aerogel skeleton structure of connection is dipped in CaCl2Aqueous solution is to carry out rapid ionomer reaction, cleaning
Fall extra Ca2+Afterwards, then secondary freeze drying is carried out.This method make full use of the fast reaction between sodium alginate and calcium ion from
And make porous sodium alginate/graphene oxide compound skeleton structure hardening.
Detailed description of the invention
Fig. 1 is oil water separation type sodium alginate/graphene oxide composite aerogel pictorial diagram.
Fig. 2 is oil water separation type sodium alginate/graphene oxide composite aerogel microscopic appearance figure, and (a) is that low range is micro-
It sees structure chart (× 50,500 μm), (b) high magnification micro-structure diagram (× 1000,10 μm).
The various oil products of Fig. 3 (can connect in oil water separation type sodium alginate/graphene oxide composite aerogel wettability of the surface
Feeler), wherein abscissa indicates the type of test oil product, and ordinate indicates contact angle size.
Specific embodiment
In order to sufficiently disclose oil water separation type sodium alginate/graphene oxide composite aerogel and its preparation side of the invention
Method, below with reference to embodiment, invention is further described in detail.
Embodiment 1, a kind of oil water separation type sodium alginate/graphene oxide composite aerogel preparation method, including with
Lower step:
(1) sodium alginate/graphene oxide liquid mixture preparation:
A, it prepares sodium alginate soln: sodium alginate being dissolved in deionized water, after 1000rpm magnetic agitation 1 hour gradually
By mixing speed be reduced to 500 rpm until its become clear solution, be made concentration be 2wt% sodium alginate soln；
B, then the graphene oxide suspension 15min that ultrasonic treatment concentration is 1wt% is added to step A alginic acid
In sodium solution, makes graphene oxide and sodium alginate mass ratio 1:10,1500rpm magnetic agitation 2h, obtain uniform seaweed
Sour sodium/graphene oxide dispersion；
(2) uncrosslinked sodium alginate/graphene oxide composite aerogel preparation:
Will equipped with sodium alginate/graphene oxide dispersion vessel obtained by step (1), be put into lyophilization system (-
15 °C, 400 μ bar) freeze-drying 48h is carried out, it is freeze-dried and the uncrosslinked compound gas of sodium alginate/graphene oxide
Gel；The vessel are culture dish.
(3) oil water separation type sodium alginate/graphene oxide composite aerogel preparation:
Sodium alginate/graphene oxide composite aerogel uncrosslinked obtained by step (2) is placed in calcium chloride solution (concentration
For 10h in 4wt%), sufficiently to carry out the reaction of calcium ion crosslinking；After reaction, using the multiple repeated flushing airsetting of deionized water
Then glue carries out secondary freeze drying to remove uncrosslinked calcium ion again, obtain oil water separation type sodium alginate/oxidation stone
Black alkene composite aerogel.
Oil water separation type sodium alginate/graphene oxide composite aerogel prepared by embodiment 1, by following test:
(1) wettability is tested
Water and oil can be used Drop Shape Analysis System in aeroge wettability of the surface and be carried out by contact angle test
Assessment.Air Zhong Shui and oil can be tested in aeroge wettability of the surface: take 5 μ L water droplets and oil droplet (test oil are as follows: coal respectively
Oil, pumping fluid, n-hexane, soybean oil and toluene) aeroge surface is instilled, using connecing for Drop Shape Analysis System tracking water
The variation of the contact angle (OCA) of feeler (WCA) and oil, assesses its aerial wetability.
The result shows that water droplet and oil droplet have just contacted aeroge surface, just penetrate into inside aeroge, is demonstrated by high quickly
Super hydrophilic and super oil-wet behavior, water and oil contact angle be 0 °.
Underwater oil can be tested in aeroge wettability of the surface: aeroge be immersed simulated seawater, with micro syringe by 5
μ L oil droplet (test oil are as follows: kerosene, pumping fluid, n-hexane, soybean oil and toluene) is injected from aeroge bottom surface, passes through test
The underwater oil of size assessment at droplets contact angle is in aeroge wettability of the surface.
The result shows that oil droplet is adhered to the lower surface of aeroge, there is no any infiltrations, and OCA is all greater than 150 °, such as attached drawing
Shown in 3, it is demonstrated by extremely strong underwater superoleophobic property.
(2) salt resistant character is tested
Aeroge is immersed into 30 days (being set to a cycle) in simulated seawater, every the primary underwater oil of test in 5 days in airsetting
The wettability on glue surface (taking kerosene is to test oil product), i.e., judge the anti-salt property of aeroge according to the variation of the contact angle of oil.
The result shows that OCA is gradually decreased from 160 ° but is all larger than 150 °, illustrate that aeroge impregnates 30 days in simulated seawater
Still there is underwater superoleophobic state afterwards, illustrate high salt tolerance.
(3) oil-aqueous mixtures separative efficiency test
Firstly, aeroge surface is pre-wetted with water, then it is fixed between two vertical glass tubes and with folder
Sub-folder is lived, and connects liquid-collecting bottle below.Apparatus above is poured into configuration oil-aqueous mixtures (V:V=1:1), is imitated to the separation of oil water mixture
Rate is tested.Wherein, test oil product includes kerosene, pumping fluid, n-hexane, soybean oil, toluene and crude oil, and water is simulation sea
Water.
The result shows that oil water separation type sodium alginate/graphene oxide composite aerogel manufactured in the present embodiment, have compared with
High oil-aqueous mixtures separating capacity is up to 99.6% to kerosene-water separative efficiency, all to other several oil product separative efficiencies
More than 98.5%.
(4) reusing is tested
Oil-aqueous mixtures separation finishes, compound to oil water separation type sodium alginate/graphene oxide manufactured in the present embodiment
Aeroge is repeatedly squeezed and is rubbed, and rinses aeroge oil droplet remained on surface with flowing water, is continued on for next time
The separation process of oil-aqueous mixtures, and separative efficiency is tested.
The result shows that oil water separation type sodium alginate/graphene oxide composite aerogel manufactured in the present embodiment, repeats benefit
Structural failure and metaboly are not found with 40 times, illustrate aeroge elasticity with higher and mechanical strength；Again to oil-
Aqueous mixtures separation process is tested, and aeroge still presents higher separative efficiency, up to 98% or more.
Embodiment 2, a kind of oil water separation type sodium alginate/graphene oxide composite aerogel preparation method, including with
Lower step:
(1) sodium alginate/graphene oxide liquid mixture preparation:
A, it prepares sodium alginate soln: sodium alginate being dissolved in deionized water, will gradually be stirred after 1200rpm magnetic agitation 1h
Mix speed be reduced to 500 rpm until its become clear solution, be made concentration be 4wt% sodium alginate soln；
B, then the graphene oxide suspension 15min that ultrasonic treatment concentration is 0.5wt% is added to step A seaweed
In acid sodium solution, make graphene oxide and sodium alginate mass ratio 0.5:10,2000rpm magnetic agitation 2h, obtains alginic acid
Sodium/graphene oxide dispersion；
(2) uncrosslinked sodium alginate/graphene oxide composite aerogel preparation:
Will equipped with sodium alginate/graphene oxide dispersion vessel obtained by step (1), be put into lyophilization system (-
15 °C, 400 μ bar) freeze-drying 48h is carried out, obtain uncrosslinked sodium alginate/graphene oxide composite aerogel.
(3) oil water separation type sodium alginate/graphene oxide composite aerogel preparation:
Sodium alginate/graphene oxide composite aerogel uncrosslinked obtained by step (2) is placed in calcium chloride solution (concentration
For 12h in 3wt%), sufficiently to carry out the reaction of calcium ion crosslinking.After reaction, using the multiple repeated flushing airsetting of deionized water
Then glue carries out secondary freeze drying to remove uncrosslinked calcium ion again, obtain oil water separation type sodium alginate/oxidation stone
Black alkene composite aerogel.
Oil water separation type sodium alginate/graphene oxide composite aerogel prepared by embodiment 2, by following test:
(1) wettability is tested
Air Zhong Shui and oil can be tested in aeroge wettability of the surface: take respectively 5 μ L water droplets and oil droplet (test oil are as follows:
Kerosene, pumping fluid, n-hexane, soybean oil and toluene) aeroge surface is instilled, water droplet is tracked using Drop Shape Analysis System
Change with the contact angle of oil droplet, assesses its aerial wetability.
The result shows that water droplet and oil droplet can penetrate into inside aeroge quickly, high super hydrophilic (WCA=0 °) is shown
With super oil-wet behavior (OCA=0 °).
Underwater oil can be tested in aeroge wettability of the surface: aeroge be immersed simulated seawater, with micro syringe by 5
μ L oil droplet (test oil are as follows: kerosene, pumping fluid, n-hexane, soybean oil and toluene) is injected from aeroge bottom surface, passes through test
The underwater oil of size assessment at droplets contact angle is in aeroge wettability of the surface.
The result shows that contact angle of the various oil products on aeroge surface is all greater than 150 °, it is demonstrated by the extremely strong water of aeroge
Under superoleophobic property.
(2) salt resistant character is tested
Aeroge is immersed into 40 days (being set to a cycle) in simulated seawater, every the primary underwater oil of test in 5 days in airsetting
The wettability on glue surface (taking kerosene is test oil), i.e., judge the anti-salt property of aeroge according to the variation of the contact angle of oil.
The result shows that increasing with number of days is impregnated, OCA is gradually decreased from 160 ° but is all larger than 150 °, illustrates that aeroge exists
Still there is underwater superoleophobic state after impregnating 40 days in simulated seawater, illustrate high salt tolerance.
(3) oil-aqueous mixtures separative efficiency test
Firstly, aeroge surface is pre-wetted with water, then it is fixed between two vertical glass tubes and with folder
Sub-folder is lived, and connects liquid-collecting bottle below.Apparatus above is poured into configuration oil-aqueous mixtures (V:V=1:1), is imitated to the separation of oil water mixture
Rate is tested.Wherein, test oil product includes kerosene, pumping fluid, n-hexane, soybean oil, toluene and crude oil, and water is simulation sea
Water.
The result shows that aeroge oil with higher-aqueous mixtures separating capacity manufactured in the present embodiment, to kerosene-water
Separative efficiency be up to 99.9%, 97% is above to other several oil product separative efficiencies.
(4) reusing is tested
Oil-aqueous mixtures separation finishes, and composite aerogel manufactured in the present embodiment is repeatedly squeezed and rubbed, is used in combination
Flowing water rinses aeroge oil droplet remained on surface, continues on for oil-aqueous mixtures separation process next time, and to separation
Efficiency is tested.
The result shows that aeroge manufactured in the present embodiment, which reuses 30 times, does not find structural failure and metaboly,
Illustrate aeroge elasticity with higher and mechanical strength；Oil-aqueous mixtures separation process is tested again, aeroge is still
Higher separative efficiency is so presented, up to 97% or more.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (5)
1. a kind of preparation method of oil water separation type sodium alginate/graphene oxide composite aerogel, it is characterised in that preparation step
It is rapid as follows:
(1) sodium alginate/graphene oxide liquid mixture preparation:
A, it prepares sodium alginate soln: sodium alginate being dissolved in deionized water, gradually will after 800 ~ 1200rpm magnetic agitation, 1 ~ 2h
Mixing speed be reduced to 500 rpm until its become clear solution, be made concentration be 1wt% ~ 4wt% sodium alginate soln；
B, then 10 ~ 20min of graphene oxide suspension that ultrasonic treatment concentration is 0.5wt% ~ 3wt% is added to step A institute
It obtains in sodium alginate soln, stirs graphene oxide and sodium alginate mass ratio 0.5:10 ~ 1:10,1200 ~ 2000rpm magnetic force
No less than 2h is mixed, sodium alginate/graphene oxide dispersion is obtained；
(2) uncrosslinked sodium alginate/graphene oxide composite aerogel preparation: will be equipped with sodium alginate/oxygen obtained by step (1)
The vessel of graphite alkene dispersion liquid, are put into lyophilization system and are freeze-dried, and acquire uncrosslinked sodium alginate/oxidation
Graphene composite aerogel；
(3) sodium alginate of calcium ion crosslinking/graphene oxide composite aerogel preparation: will be uncrosslinked obtained by step (2)
Sodium alginate/graphene oxide composite aerogel is placed in the calcium chloride solution that concentration is 2wt%-4wt%, after reacting 8-12h, is adopted
With the multiple repeated flushing aeroge of deionized water, secondary freeze drying is then carried out, obtains sodium alginate/oxygen of calcium ion crosslinking
Graphite alkene composite aerogel.
2. a kind of preparation side of oil water separation type sodium alginate/graphene oxide composite aerogel according to claim 1
Method, it is characterised in that magnetic agitation rotating speed described in step (1) is 1000rpm, and the addition concentration of graphene oxide suspension is 1
Wt%, sodium alginate soln concentration are 2 wt%, and the graphene oxide and sodium alginate mass ratio are 1:10, the ultrasound
The processing time is 15min.
3. a kind of preparation side of oil water separation type sodium alginate/graphene oxide composite aerogel according to claim 1
Method, it is characterised in that step (2) vessel are culture dish, and freeze-drying temperature is -15 °C, and absolute pressure is 400 μ bar, cold
Jelly drying time is 48h.
4. a kind of preparation side of oil water separation type sodium alginate/graphene oxide composite aerogel according to claim 1
Method, it is characterised in that step (3) described calcium chloride solution, concentration are 4 wt%, and the time for immersing ionic calcium soln is 10h.
5. by oil water separation type sodium alginate/compound gas of graphene oxide of the described in any item method preparations of claim 1-4
Gel.
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| CN112023895A (en) * | 2020-08-26 | 2020-12-04 | 山东大学 | Adjustable and controllable amphiphilic enteromorpha/graphene composite aerogel, preparation method thereof and application thereof in oil-water separation |
| CN112107887A (en) * | 2020-08-26 | 2020-12-22 | 广东工业大学 | Underwater super-oleophobic oil-water separation material and preparation method and application thereof |
| CN114843006B (en) * | 2022-05-27 | 2024-02-06 | 四川大学 | Three-dimensional flexible sensor material and preparation method and application thereof |
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| CN105566659B (en) * | 2015-12-25 | 2018-07-03 | 郑州轻工业学院 | A kind of graphene oxide/nano-cellulose aerogel and its preparation method and application |
| CN105601983B (en) * | 2016-03-10 | 2020-09-15 | 云南中烟工业有限责任公司 | Natural polysaccharide aerogel, preparation method thereof and application thereof in cigarettes |
| CN105797685A (en) * | 2016-05-09 | 2016-07-27 | 江苏大学 | Preparation method of sodium alginate-graphene oxide macroscopic sphere composite material |
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